Distribution of an antioxidant in polypropylene/ethylene-octene copolymer blends studied by atomic force microscopy-infrared.

In this work, the microscopic distribution of antioxidant 1010 (AT1010) in blends of isotactic polypropylene (iPP) with an ethylene-octene copolymer (POE) was investigated in situ using the atomic force microscopy-infrared (AFM-IR) technique. Pellets of an iPP/POE blend containing AT1010 at a mass ratio of 79.5 : 20 : 0.5 were extruded at different screw speeds, and were then injection-molded into plates. The domain size of the POE disperse phase in the pellets was about 1 µm, regardless of the screw speed, and remained unchanged in the injection molding. AFM-IR analyses revealed that AT1010 preferred to stay in the POE disperse phase rather than in the iPP matrix, with a concentration ratio of ∼1.2 in the extruded pellets independent of the screw speed, which was further increased to ∼1.5 in the molded plates. The preferred concentration of AT1010 in the POE was in line with its higher solubility in rubber than in iPP, and the enhanced partition of AT1010 in the molded plates was attributed to a longer processing time in the molten state than that for the extruded pellets, which was verified by AFM-IR analyses of pellets extruded with different residence times.

Mechanisms Affecting Physical Aging and Swelling by Blending an Amphiphilic Component.

Polymer blending is a promising method to overcome stability obstacles induced by physical aging and swelling of implant scaffolds prepared from amorphous polymers in biomedical application, since it will not bring potential toxicity compared with chemical modification. However, the mechanism of polymer blending still remains unclearly explained in existing studies that fail to provide theoretical references in material R&D processes for stability improvement of the scaffold during ethylene oxide (EtO) sterilization, long-term storage, and clinical application. In this study, amphiphilic poly(ethylene glycol)-co-poly(lactic acid) (PELA) was blended with amorphous poly(lactic-co-glycolic acid) (PLGA) because of its good miscibility so as to adjust the glass transition temperature (Tg) and hydrophilicity of electrospun PLGA membranes. By characterizing the morphological stability and mechanical performance, the chain movement and the glass transition behavior of the polymer during the physical aging and swelling process were studied. This study revealed the modification mechanism of polymer blending at the molecular chain level, which will contribute to stability improvement and performance adjustment of implant scaffolds in biomedical application.

Neutron Total Scattering Investigation of the Dissolution Mechanism of Trehalose in Alkali/Urea Aqueous Solution.

The atomic picture of cellulose dissolution in alkali/urea aqueous solution is still not clear. To reveal it, we use trehalose as the model molecule and total scattering as the main tool. Three kinds of alkali solution, i.e., LiOH, NaOH and KOH are compared. The most probable all-atom structures of the solution are thus obtained. The hydration shell of trehalose has a layered structure. The smaller alkali ions can penetrate into the glucose rings around oxygen atoms to form the first hydration layer. The larger urea molecules interact with hydroxide groups to form complexations. Then, the electronegative complexation can form the second hydration layer around alkali ions via electrostatic interaction. Therefore, the solubility of alkali aqueous solution for cellulose decreases with the alkali cation radius, i.e., LiOH > NaOH > KOH. Our findings are helpful for designing better green solvents for cellulose.

Interplay between Caging and Bonding in Binary Concentrated Colloidal Suspensions.

When a liquid becomes dynamically arrested, a gel, a repulsive glass, or an attractive glass state will form. Bonding and caging mechanisms decide their static structures and dynamic properties. To better understand their interplay, the competition between bonding and caging in a binary mixture of polystyrene core/poly( N-isopropylacrylamide) shell (CS) microgels and sulfonated polystyrene (PSS) particles is studied. CS microgels have short-range attraction above the volume phase transition temperature, whereas PSS species experiences relatively long-range electrostatic repulsion. Adding more PSS into the binary mixture will, of course, increase the total effective volume fraction but lead to different properties in gel or glass states. For instance, in gels, it increases the localization length and weakens the gel, whereas in glass, it decreases the localization length and strengthens the glass. This thus implies that the static and dynamic properties of gels are mainly controlled by bonding and those of both repulsive and attractive glasses are governed by caging. On the other hand, increasing the temperature will decrease the effective volume fraction because of the volume phase transition of the CS microgels. A discontinuous repulsive glass-to-liquid-to-gel transition can be observed when the PSS concentration is low, but a continuous repulsive glass-to-gel transition can also be observed with the increase of the PSS concentration. This may hint that glass transition and physical gelation share a similar mechanism, whereas the former has a longer relaxation time.

Tuning the bridging attraction between large hard particles by the softness of small microgels.

In this study, the attraction between large hard polystyrene (PS) spheres is studied by using three types of small microgels as bridging agents. One is a purely soft poly(N-isopropylacrylamide) (PNIPAM) microgel, the other two have a non-deformable PS hard core surrounded by a soft PNIPAM shell but are different in the core-shell ratio. The affinity for bridging the large PS spheres is provided and thus affected by the PNIPAM constituent in the microgels. The bridging effects caused by the microgels can be indirectly incorporated into their influence on the effective attraction interaction between the large hard spheres, since the size of the microgels is very small in comparison to the size of the PS hard spheres. At a given volume fraction of large PS spheres, they behave essentially as hard spheres in the absence of small microgels. By gradually adding the microgels, the large spheres are connected to each other through the bridging of small particles until the attraction strength reaches a maximum value, after which adding more small particles slowly decreases the effective attraction strength and eventually the large particles disperse individually when saturated adsorption is achieved. The aggregation and gelation behaviors triggered by these three types of small microgels are compared and discussed. A way to tune the strength and range of the short-range attractive potential via changing the softness of bridging microgels (which can be achieved either by using core-shell microgels or by changing the temperature) is proposed.

Asymmetrical phase separation and gelation in binary mixtures of oppositely charged colloids.

Two types of colloidal particles, which are nearly the same in chemical composition but carry opposite surface charges, are mixed in water. Depending on the relative proportion of the oppositely charged particles, the process of aggregation leads to the formation of discrete clusters of various sizes in dilute dispersions, and to the development of particle gel networks in more concentrated systems. Due to the significant difference in the absolute values of surface charges (negative particle: -48 mV, positive particle: +24 mV), the phase separation and the gelation behaviors are asymmetric with respect to the mixing ratio. Mixtures with excess negative particles are more stable, while mixtures with excess positive particles are easily affected by phase separation. The hetero-aggregation triggered by the addition of microscopically large macro-ions is similar to what is often observed in a mono-component charged colloidal system, i.e., phase separation occurs through addition of small electrolyte ions. Within the concentration region investigated here, it is clear that the gel line is buried inside the phase separation region. Gelation occurs only when the number and size of the clusters are large and big enough to connect up into a space-spanning network. Our results indicate that, in this binary mixture of oppositely charged colloids, although the interaction between unlike species is attractive and that between like species is repulsive, the onset of gelation is in fact governed by the equilibrium phase separation, as in the case of purely attractive systems with short-range isotropic interaction.

A Biodegradable Trilayered Barrier Membrane Composed of Sponge and Electrospun Layers: Hemostasis and Antiadhesion.

Placing a physical barrier between the injured site and the adjacent tissues is a very common and highly effective approach to prevent abdominal adhesions in these days. A biodegradable trilayered barrier was fabricated to prevent formation of abdominal adhesions, in which a poly(lactide-co-glycolide)/poly(lactide)-b-poly(ethylene glycol) (PLGA/PLA-b-PEG) electrospun layer was sandwiched between layers of carboxymethyl chitosan (CMCS) sponge. The hydrophilic CMCS sponge layers with glycerin (GL) could adhere to the surface of wound easily, and present great hemostatic capability. The mechanism of the formation of adhesion related to blood clots acting with fibroblast cells was evaluated in detail. The blood clot acted as a "medium" inducing the fibroblast cells growth and proliferation, but had no special attraction on epithelial cells. CMCS sponge layer took away the blood clots during the swelling and dissolution stages. The electrospun layer promoted the growth of epithelial cells, but exhibited inhibition on the adhesion and spread of fibroblast cells, which ensured excellent effect of adhesion prevention. Evaluated by a rat model of sidewall defect-bowel abrasion, significant reductions of postoperative adhesion in its level and occurrence were observed in animals treated by the trilayered barrier.

Coupling of gelation and glass transition in a biphasic colloidal mixture-from gel-to-defective gel-to-glass.

The state transition from gel to glass is studied in a biphasic mixture of polystyrene core/poly(N-isopropylacrylamide) shell (CS) microgels and sulfonated polystyrene (PSS) particles. At 35 °C, the interaction between CS microgels is due to short-range van der Waals attraction, while that between PSS particles is from long-range electrostatic repulsion. During the variation of the relative ratio of the two species at a fixed apparent total volume fraction, the mixture exhibits a gel-to-defective gel-to-glass transition. When small amounts of PSS are introduced into the CS gel network, some of them are kinetically trapped, causing a change in its fractal structure, and act as defects to weaken the macroscopic gel strength. An increase of the PSS content in the mixture promotes the switch from the gel to the defective gel, e.g., the typical two-step yielding gel merges into one-step yielding. This phenomenon is an indication that inter-cluster bond breakage coincides with intra-cluster bond fracture. As the relative volume fraction of PSS exceeds a critical threshold, the gel network can no longer be formed; hence, the mixture exhibits characteristics of glass. A state diagram of the biphasic mixture is constructed, and the landscapes of the different transitions will be described in future studies.

Gelation of large hard particles with short-range attraction induced by bridging of small soft microgels.

In this study, mixed suspensions of large hard polystyrene microspheres and small soft poly(N-isopropylacrylamide) microgels are used as model systems to investigate the static and viscoelastic properties of suspensions which go through liquid to gel transitions. The microgels cause short-range attraction between microspheres through the bridging and depletion mechanism whose strength can be tuned by the microgel concentration. Rheological measurements are performed on suspensions with the volume fraction (Φ) of microspheres ranging from 0.02 to 0.15, and the transitions from liquid-like to solid-like behaviors triggered by the concentration of microgels are carefully identified. Two gel lines due to bridging attraction under unsaturated conditions are obtained. Ultra-small angle neutron scattering is used to probe the thermodynamic properties of suspensions approaching the liquid-solid transition boundaries. Baxter's sticky hard-sphere model is used to extract the effective inter-microsphere interaction introduced by the small soft microgels. It is found that the strength of attraction (characterized by a single stickiness parameter τ) on two gel lines formed by bridging is very close to the theoretical value for the spinodal line in the τ-Φ phase diagram predicted by Baxter's model. This indicates that the nature of the gel state may have the same thermodynamic origins, independent of the detailed mechanism of the short-range attraction. The relationship between the rheological criterion for the liquid-solid transition and the thermodynamic criterion for the equilibrium-nonequilibrium transition is also discussed.

From repulsive to attractive glass: A rheological investigation.

Linear rheological properties and yielding behavior of polystyrene core and poly (N-isopropylacrylamide) (PNIPAM) shell microgels were investigated to understand the transition from repulsive glass (RG) to attractive glass (AG) and the A3 singularity. Due to the volume phase transition of PNIPAM in aqueous solution, the microgel-microgel interaction potential gradually changes from repulsive to attractive. In temperature and frequency sweep experiments, the storage modulus (G') and loss modulus (G″) increased discontinuously when crossing the RG-to-AG transition line, while G' at low frequency exhibited a different volume fraction (Φ) dependence. By fitting the data of RG and AG, and then extrapolating to high volume fraction, the difference between RG and AG decreased and the existence of A3 singularity was verified. Dynamic strain sweep experiments were conducted to confirm these findings. RG at 25 °C exhibited one-step yielding, whereas AG at 40 °C showed a typical two-step yielding behavior; the first yielding strain remained constant and the second one gradually decreased as the volume fraction increased. By extrapolating the second yield strain to that of the first one, the predicted A3 singularity was at 0.61 ± 0.02. At 37 °C, when Φeff = 0.59, AG showed one step yielding as the length of the attractive bond increased. The consistency and agreement of the experimental results reaffirmed the existence of A3 singularity, where the yielding behavior of RG and AG became identical.

Characterization on the phase separation behavior of styrene-butadiene rubber/polyisoprene/organoclay ternary blends under oscillatory shear.

The present work investigated the influence of organoclay (organo-montmorillonite, OMMT) on the phase separation behavior and morphology evolution of solution polymerized styrene-butadiene rubber (SSBR)/low vinyl content polyisoprene (LPI) blends with rheological methodology. It was found that the incorporation of OMMT not only reduced the droplet size of the dispersion phase, slowed down the phase separation kinetics, also enlarged the processing miscibility window of the blends. The determination on the wetting parameters indicated that due to the oscillatory shear effect, the OMMT sheets might localize at the interface between the two phases and act as compatibilizer or rigid barrier to prevent domain coarsening, resulting in slow phase separation kinetics, small droplet size, and stable morphology. The analysis of rheological data by the Palierne model provided further confirmation that the addition of OMMT can decrease the interfacial tension and restrict the relaxation of melt droplets. Therefore, a vivid "sea-fish-net" model was proposed to describe the effect of OMMT on the phase separation behavior of SSBR/LPI blends, in which the OMMT sheets acted as the barrier (net) to slow down the domain coarsening/coalescence in phase separation process of SSBR/LPI blends.

Interpretation of hip fracture patterns using areal bone mineral density in the proximal femur.

INTRODUCTION: Bone mineral density scans are currently interpreted based on an average score of the entire proximal femur. Improvements in technology now allow us to measure bone density in specific regions of the proximal femur. The study attempts to explain the pathophysiology of neck of femur (NOF) and intertrochanteric/basi-cervical (IT) fractures by correlating areal BMD (aBMD) scores with fracture patterns, and explore possible predictors for these fracture patterns. MATERIALS AND METHODS: This is a single institution retrospective study on all patients who underwent hip surgeries from June 2010 to August 2012. A total of 106 patients (44 IT/basi-cervical, 62 NOF fractures) were studied. The data retrieved include patient characteristics and aBMD scores measured at different regions of the contralateral hip within 1 month of the injury. Demographic and clinical characteristic differences between IT and NOF fractures were analyzed using Fisher's Exact test and two-sample t test. Relationship between aBMD scores and fracture patterns was assessed using multivariable regression modeling. RESULTS: After adjusted multivariable analysis, T-Troc and T-inter scores were significantly lower in intertrochanteric/basi-cervical fractures compared to neck of femur fractures (P = 0.022 and P = 0.026, respectively). Both intertrochanteric/basi-cervical fractures (mean T.Tot -1.99) and neck of femur fractures (mean T.Tot -1.64) were not found to be associated with a mean T.tot less than -2.5. However, the mean aBMD scores were consistently less than -2.5 for both intertrochanteric/basi-cervical fractures and neck of femur fractures. Gender and calcium intake at the time of injury were associated with specific hip fracture patterns (P = 0.002 and P = 0.011, respectively). CONCLUSIONS: Hip fracture patterns following low energy trauma may be influenced by the pattern of reduced bone density in different areas of the hip. Intertrochanteric/basi-cervical fractures were associated with significantly lower T-Troc and T-Inter scores compared to neck of femur fractures, suggesting that the fracture traversed through the areas with the lowest bone density in the proximal femur. In the absence of reduced T.Troc and T.Inter, neck of femur fractures occurred more commonly. T-Total scores may underestimate the severity of osteoporosis/osteopenia and measuring T-score at the neck of femur may better reflect the severity of osteoporosis and likelihood of a fragility fracture.

Crystallization-driven surface segregation and surface structures in poly(L-lactide)-block-poly(ethylene glycol) copolymer thick films.

In this work, we used poly(L-lactide)-block-poly(ethylene glycol) (PLLA-b-PEG) copolymer thick films to investigate the effect of crystallization on surface segregation, surface crystal orientation, and morphology by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), reflection optical microscopy (ROM), and two-dimensional grazing incident wide-angle X-ray scattering (2D GIWAXS) methods. ATR-FTIR results indicated that the surface fraction of PLLA block increased from 0.48 to 0.79 when T(c,PLLA) increased from 70 to 110 °C. Polarized ATR-FTIR and 2D GIWAXS results indicated that PLLA crystal lamellae preferentially oriented parallel to the film surface with increasing T(c,PLLA). The surface crystallinity of PLLA was almost independent of T(c,PLLA), while the surface crystallinity of PEG decreased with increasing T(c,PLLA). On the basis of surface crystal orientation and crystallization kinetics, we suggested that the excess of PLLA component at the surface was mainly dominated by a coupling effect of crystallization behavior and surface segregation.

Shear-thickening in mixed suspensions of silica colloid and oppositely charged polyethyleneimine.

The liquid-gel-liquid transition tuned by increasing concentration of linear and hyperbranched polyethyleneimine in suspension of silica colloids, and the accompanying shear-thickening phenomena, were investigated by rheological measurements. The influence from linear and hyperbranched polymer conformation and from different size-ratio between particle and polymer on the rheological properties of suspensions flocculated by absorbing polyelectrolyte were considered. Charge neutralization and bridging mechanism are the main reasons for the flocculation of silica colloid in this study. Because of charge reversal, the irreversible bridges are turned into flexible reversible bridges with increasing adsorption amount of oppositely charged polymer, which leads to an abrupt transition from gel to liquid. Over a narrow composition range, around the gel to liquid transition region, shear-thickening flow is observed. It is found that, for given particle volume fraction, the composition region exhibiting shear-thickening for mixed suspension with linear polyethyleneimine is broader than that for mixed suspension with hyperbranched polyethyleneimine, and the onset of shear-thickening depends only on size-ratio, regardless of the actual size of particle and polymer in the range of this study. The relationship between the gel to liquid transition and shear-thickening was discussed.

Yielding behavior in colloidal glasses: comparison between "hard cage" and "soft cage".

Rheological measurements are utilized to examine the yielding behavior of a polystyrene (PS) core and poly(N-isopropylacrylamide) (PNIPAM) shell microgel system with varying shell/core ratio. For a shell/core ratio of 0.15 at high concentrations, the suspensions show a typical hard sphere (HS) yielding response where the loss modulus (G″) exhibits a single peak due to cage breaking. As a result of tighter cages and less cage distortion prior to yielding, the peak location of G″ decreases with volume fraction. For a shell/core ratio of 1.10, which behaves like a soft jammed glass at high concentration, the suspensions exhibit a one-step yielding behavior similar to that of HS glass. However, the location of the peak in G″ increases with volume fraction, demonstrating the important role of particle deformation in the breakage of cages. For an intermediate shell/core ratio of 0.34, the system displays a two-step yielding behavior, as observed in previous reports for attractive glasses. By increasing the volume fraction, the strain of the first peak increases while the second one decreases. In addition, as the effective volume fraction increases to 112%, the two peaks merge into one broad peak. It is demonstrated that the first peak of G″ is due to deformation of the shell, and the second peak of G″ is attributed to cage breaking as a result of the cores colliding with each other. Combining these results, a yielding state diagram from typical HS to soft jammed glass is demonstrated.

Bridging and caging in mixed suspensions of microsphere and adsorptive microgel.

Gelation and glass transition in a mixed suspension of polystyrene (PS) microsphere and poly(N-isopropylacrylamide) (PNIPAM) microgel were studied as a function of the total colloid volume fraction and mixing ratio of these two components. The PNIPAM microgel, which is adsorbable on the PS microsphere surface, can induce bridging or stabilizing effect between microspheres depending on whether the volume fraction of microgel (ΦMG) is smaller or larger than the saturated adsorption concentration (Φ*MG) for a given volume fraction of the microsphere (ΦMS). Φ*MG is in a linear relationship with ΦMS, and the value of ΦMG/Φ*MG can be taken as an approximate measure of surface coverage. A state diagram of gelation and glass transition is constructed with the short-ranged attractive interaction, resulting from the well-defined bridging bonding. Keeping ΦMG/Φ*MG = 0.20 and increasing ΦMS from 0.25 to 0.55, the mixed suspension transforms from a bridging gel into an attractive glass; moreover, while keeping ΦMS = 0.45 and increasing ΦMG/Φ*MG from 0.20 to 1.2, the mixed suspension changes from a bridging gel into an attractive glass, and then to a repulsive glass. The bridging effect and the cage effect can be distinguished by the yielding behaviors in rheological measurements. In the nonlinear dynamic rheological experiments, one-step yielding, corresponding to the disconnecting of bridge network, is observed in the bridging gel, and one-step yielding, corresponding to the breaking of cage, is observed in the repulsive glass. However, a two-step yielding behavior is found in the bridging-induced attractive glass, which is attributed to the bridging effect of microgels and the caging effect of the dense environment.

Hierarchical coarsening in the late stage of viscoelastic phase separation.

Coarsening is a general phenomenon in phase separating mixtures. In this study, we report a hierarchical coarsening at different length scales. Dispersed domains grew by direct combination of two/three small ones while some small domains can survive for a long time. The small angle laser light scattering showed that the scattered intensity exhibited multiple "decay-growth" transitions in the coarsening process. The evolution of the main peak gave a characteristic power law index of about -3/4, which is much faster than the -1/3 relationship from the traditional theories. We propose that relaxation and hydrodynamic flow play important roles in this process.

Effects of particle softness on shear thickening of microgel suspensions.

A series of microgel particles composed of a polystyrene (PS) core and a thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) shell with different shell thicknesses were investigated to elucidate the effect of microgel softness on its shear thickening behavior. Since the softness of the microgels increases with decreasing temperature through the volume phase transition effect of PNIPAM shell, the measured softness parameter, n, which is derived from the Zwanzig-Mountain equation, was used to measure and describe the combined influences of temperature and shell thickness. Confocal microscopy is used to investigate the interaction potential between microgel particles with different softness parameters. According to the obtained results, the softness parameter can provide an estimate for the shear thickening behavior of microgel suspensions, at least semi-quantitatively.

Perspectives on the Novel Multifunctional Nerve Guidance Conduits: From Specific Regenerative Procedures to Motor Function Rebuilding.

Peripheral nerve injury potentially destroys the quality of life by inducing functional movement disorders and sensory capacity loss, which results in severe disability and substantial psychological, social, and financial burdens. Autologous nerve grafting has been commonly used as treatment in the clinic; however, its rare donor availability limits its application. A series of artificial nerve guidance conduits (NGCs) with advanced architectures are also proposed to promote injured peripheral nerve regeneration, which is a complicated process from axon sprouting to targeted muscle reinnervation. Therefore, exploring the interactions between sophisticated NGC complexes and versatile cells during each process including axon sprouting, Schwann cell dedifferentiation, nerve myelination, and muscle reinnervation is necessary. This review highlights the contribution of functional NGCs and the influence of microscale biomaterial architecture on biological processes of nerve repair. Progressive NGCs with chemical molecule induction, heterogenous topographical morphology, electroactive, anisotropic assembly microstructure, and self-powered electroactive and magnetic-sensitive NGCs are also collected, and they are expected to be pioneering features in future multifunctional and effective NGCs.

Liquid-gel-liquid transition and shear thickening in mixed suspensions of silica colloid and hyperbranched polyethyleneimine.

The rheological property of mixed suspensions of silica colloid and hyperbranched polyethyleneimine (hPEI) was studied as functions of particle volume fraction, ratio of polymer to particle, and pH value. A mechanism of liquid-gel-liquid transition for this mixed system was proposed based on the amount and the conformation of polyelectrolyte bridges which were able to self-arrange with solution environments. The hPEI, which is adsorptive to the surface of silica colloid, can induce bridging or stabilizing effect between particles depending on whether the concentration of hPEI (Cp) is smaller or larger than the equilibrium adsorbed amount (Cp*) for a given volume fraction of particles. In dilute colloid suspensions, the Cp* can be determined by dynamic light scattering as the correlation function returns back to a narrow distributing single relaxation with increasing Cp. In concentrated colloid suspensions, the Cp* can be determined by rheological measurement as gel-liquid transition occurs with increasing Cp. The Cp* is an important concentration ratio of polymer to particle denoting the transition of irreversible and reversible bridging. For mixed suspensions at equilibrium adsorbed state (Cp ≈ Cp*), the adsorption-desorption of polymer bridges on the particles can reversibly take place, and shear thickening is observed under a steady shear flow as a result of rapid extension of bridges when the relaxation time scale of extension is shorter than that of desorption.